CN103480434B - A kind of wet method vulcanization process of hydrogenation catalyst - Google Patents
A kind of wet method vulcanization process of hydrogenation catalyst Download PDFInfo
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- CN103480434B CN103480434B CN201310402405.3A CN201310402405A CN103480434B CN 103480434 B CN103480434 B CN 103480434B CN 201310402405 A CN201310402405 A CN 201310402405A CN 103480434 B CN103480434 B CN 103480434B
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Abstract
The present invention relates to a kind of wet method sulfuration of catalyst used for hydrogenation of distilled oil fraction.The method adopts wet method sulfuration in device, and system introduces direct steaming gasoline and new hydrogen, and maintenance hydrogen-oil ratio is 180-300Nm
3/ m
3vulcanizing agent injects catalytic gasoline pump and heavy petrol reaction feed pump intake place mixes with direct steaming gasoline, counterweight gasoline hydrogenation reactor, pre-hydrogenation deactivation reaction of Salmon-Saxl device and selective hydrogenation reactor inner catalyst carry out sulfuration successively, wherein vulcanizing agent injection rate is 20-90kg/h, with the sulfuration of multistage vulcanization mode, reach high cure efficiency, there is shorter cure time simultaneously, go into operation steadily.
Description
Technical field
The present invention relates to vulcanization process and application that a kind of hydrogenation catalyst is provided, particularly a kind of wet method vulcanization process of catalyst used for hydrogenation of distilled oil fraction.
Background technology
In oil unifining process, because its hydrogenation catalyst exists mainly with the oxidation states of VIB and group VIII metal element (as W, Co, Mo, Ni etc.) greatly, cause the hydrogenation activity of catalyst low, poor stability.The fact shows, when in catalyst, metal only exists with sulphided state, the activity of hydrogenation catalyst just can obtain best performance, so catalyst all must carry out sulfuration before use.
Usual industrial conventional vulcanization process has the dry pre-sulfiding and large class of wet method sulfuration two.Dry pre-sulfiding is in presence of hydrogen, directly by CS
2or other organic sulfur compounds are injected in reaction system and carry out gas-phase presulfiding, in this sulfidation, only use vulcanizing agent, need to introduce when reaction bed temperature being reduced to safe temperature the low nitrogen oil that goes into operation after sulfuration terminates and carry out catalyst irrigation, then heat up and progressively switch feedstock oil, on-stream time is longer, under prerequisite completely smoothly, usually from sulfuration at least need more than 6 days to complete swap-in feedstock oil, and exist and be easy to that larger temperature fluctuation etc. occurs and be unfavorable for quiet run factor.Wet method sulfuration is generally also referred to as liquid phase sulfuration, and a kind of sulfuration namely adopting the sulfurized oil containing sulfide to carry out under liquid phase or semi-liquid phase state, has the sulfide added by outside to carry out sulfuration and rely on the sulfide of petroleum distillate self to carry out sulfuration two kinds of modes.Compare dry pre-sulfiding, because mass transfer in liquid phase heat-transfer environment is relatively good, sulfidation is easier to control.
Patent CN1082591A discloses a kind of processing hydrocarbons catalyst wet vulcanization process, this method by containing the solvent containing alkene or alkene cut and catalyst and sulfurizing agent, the exothermic effect produced when significantly can reduce presulfurization.But the method adds vulcanizing agent in solvent, and cure time is longer, increase the carbon deposit on catalyst, reduce catalytic activity.
Patent CN1362289A discloses a kind of vulcanization process of hydrogenation catalyst, and the method by arranging the one or more sulfuration of hydrogen sulfide generator for catalyst of having loaded the sulphur-containing substance such as troilite or elemental sulfur before hydrogenation reactor.Its shortcoming needs to build a reactor separately, and need to purify hydrogen sulfide gas, need the make-up hydrogen compressor of hydrogen sulfide corrosion resistant, sulphur iron ore also needs subsequent treatment simultaneously.
Patent US4177136 discloses the hydroprocessing processes with elementary sulfur, hydrogenation catalyst being carried out to sulfuration, carries out sulfuration with elementary sulfur to catalyst.The method shortcoming is that solid element sulphur is all converted into hydrogen sulfide at a lower temperature, but catalyst at low temperatures can not sulfuration complete, can not supply catalyst enough sulphur during high temperature, namely the feed speed of hydrogen sulfide can not control accurately, makes the cure efficiency of catalyst poor.
In a word, wet method sulfidation is faced with a following difficult problem: (1) distillate easily decomposes the more unsaturated hydrocarbons of generation in the reaction, and cure time is longer, and the carbon deposit on catalyst can increase; (2) time of needing in the sulfidation of catalyst of liquid-phase hydrogenatin treatment process is longer, and the hydrogen sulfide caused due to hydrogen supply rate deficiency when simultaneously there occurs catalyst vulcanization is not enough and the insufficient phenomenon of catalyst vulcanization that produces; (3) the catalyst vulcanization outlet temperature due to high tenor is unsuitable too high, is generally 320 DEG C, and existing can not the defect of full cure, especially for tungsten-containing catalyst usually need higher curing temperature could sulfuration complete, catalyst activity is affected.
Summary of the invention
For above deficiency, the object of this invention is to provide a kind of newly, the vulcanization process that can improve catalyst vulcanization effect further, the effect of the operation that steadily goes into operation that reaches reduction energy consumption, shorten the catalyst vulcanization time, reaches.The vulcanization process of the present invention to catalyst comprises following content:
1. sulfuration adopts wet method sulfuration in device, if facility such as note sulphur agent pump and vulcanizing agent tank etc.During sulfuration, introduce direct steaming gasoline and enter device, enter reaction system from raw material surge tank and heavy naphtha surge tank, introduce new hydrogen and set up hydrogen circulation, maintaining system hydrogen-oil ratio is 180-300 Nm
3/ m
3;
2. vulcanizing agent enters catalytic gasoline pump and heavy petrol reaction feed pump intake mixes with direct steaming gasoline by noting sulphur infusion, through normal reaction flow process, counterweight gasoline hydrogenation reactor, pre-hydrogenation deactivation reaction of Salmon-Saxl device and selective hydrogenation reactor inner catalyst carry out sulfuration successively.
3. catalyst vulcanization program is divided into one-level sulfuration and secondary sulfuration:
(1) one-level sulfuration, rises to 200-280 DEG C with 10-20 DEG C/h by reactor inlet temperature, constant temperature 5-24h.Vulcanizing agent injection rate is 20-90 kg/h, keeps H
2s content is about 1-2mol%.Require to control sulfuration in following scope:
A, any catalyst bed maximum temperature are no more than 280 DEG C;
B, be no more than 20 DEG C by any catalyst bed temperature rise;
C, be no more than 2wt% sulphur to total reactor feed
(2) secondary sulfuration, rises to 280-320 DEG C with 15 DEG C/h by reactor inlet temperature, keeps 5-24 h.Keep vulcanizing agent injection rate, make circulating air content be 1-2mol%, overall cure time is 10-48 h.
4., after heavy petrol hydrogenation reaction product flows through heat exchanger heat exchange, through heavy fractioning hydrogenation product air cooler, the cooling of heavy fractioning hydrogenation product aftercooler, enter cold high pressure separator and carry out gas-liquid separation.
5. vulcanizing agent described in the present invention can be elemental sulfur, inorganic or organosulfur compound.The condition preferably met can be analyzed to H under lower reaction temperature
2s, to improve cure efficiency; And cost is low, toxicity is little, to reduce cost, improves security.Can select mercaptan, disulphide, polysulfide and thiophenic acid compound by described requirement vulcanizing agent, comparatively conventional is carbon disulfide, dimethyl disulfide and DMDS;
6. the present invention goes for the wet method sulfidation of any hydrogenation catalyst, be specially adapted to liquid phase hydrogenating catalyst sulfuration;
7. conditions of vulcanization of the present invention is constant temperature 5-24h at 200-280 DEG C, constant temperature 5-24h at 280-320 DEG C, and heating rate is 10-20 DEG C/h; Vulcanizing agent injection rate is 20-90 kg/h, and cure time is 10-48h.
8. energy supply of the present invention is provided by following equipment.Heavy petrol hydrogenation reactor heat is provided by reaction feed stove, and pre-hydrogenation deactivation reaction of Salmon-Saxl device heat, through selective hydrogenation product/heavy fractioning hydrogenation product exchanger, is provided by heavy fractioning hydrogenation product; Selective hydrogenation reactor institute calorific requirement, through catalytic gasoline/pre-hydrogenation product exchanger, is provided by pre-hydrogenation products;
Detailed description of the invention
Method of the present invention is specific as follows: during sulfuration, introduces direct steaming gasoline and enters device, enter reaction system from raw material surge tank and heavy naphtha surge tank, introduces new hydrogen and sets up hydrogen circulation.Then heat up, when temperature reaches vulcanizing agent decomposition temperature, enter vulcanizing agent by note sulphur infusion, mix with direct steaming gasoline, with 10-20 DEG C/h, reactor inlet temperature is risen to 200-280 DEG C, constant temperature 5-24 h.Vulcanizing agent injection rate is 20-90 kg/h, keeps H
2s content is about 1-2mol%.With 15 DEG C/h, reactor inlet temperature is risen to 280-320 DEG C subsequently, keep vulcanizing agent injection rate, make circulating air content be 1-2mol%, constant temperature sulfuration 5-24 h, completes the sulfidation of catalyst.In sulfidation of the present invention, other content is well known to those skilled in the art.
Concrete condition of the present invention is further illustrated below by embodiment.Select different catalyst A, B in embodiment, its physicochemical property is in table 1, and the reaction process condition of embodiment and effect are respectively in table 2, table 3.
The physicochemical property of table 1 catalyst
Table 2 embodiment process conditions
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Catalyst | A | A | B | B |
| Hydrogen to oil volume ratio | 200 | 250 | 220 | 260 |
| Vulcanizing agent | DMDS | CS 2 | DMDS | CS 2 |
| Heating rate DEG C/h | 10 | 15 | 10 | 15 |
| One-level curing temperature/DEG C | 220 | 250 | 220 | 250 |
| Vulcanizing agent injection rate kg/h | 30 | 35 | 25 | 30 |
| One-level cure time/h | 5 | 12 | 10 | 24 |
| Secondary curing temperature/DEG C | 280 | 300 | 280 | 300 |
| Secondary cure time/h | 5 | 12 | 10 | 24 |
| Sulfuration total time/h | 10 | 24 | 20 | 48 |
The reaction effect of table 3 embodiment
| Feedstock oil | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Total sulfur, μ g/g | 856 | --- | --- | 48 | 39 |
| Mercaptan, μ g/g | 38 | --- | --- | 5 | 4 |
| Alkadienes, v% | 1.6 | 0.35 | 0.25 | --- | --- |
| Alkene, v% | 34 | 18.5 | 17.6 | --- | --- |
| Colloid mg/100mL | 7 | 1.6 | 1.5 | --- | --- |
| Olefin removal rate | --- | 46% | 48% | --- | --- |
| Total sulfur removal rate | --- | --- | --- | 94% | 95% |
As can be seen from embodiment, adopt catalyst vulcanization method of the present invention, olefin removal rate > 45%, desulfurization degree > 90%, not only effectively can play the catalytic activity of catalyst, and cure time controls, within 48 h, to shorten on-stream time, improves the stability in sulfidation.
Claims (1)
1. a wet method vulcanization process for hydrogenation catalyst, is characterized in that comprising the steps:
When A, sulfuration, introduce direct steaming gasoline and enter device, enter reaction system from raw material surge tank and heavy naphtha surge tank, introduce new hydrogen and set up hydrogen circulation;
B, vulcanizing agent are mixed with direct steaming gasoline by the porch of noting sulphur infusion and enter catalytic gasoline pump and heavy petrol reaction feed pump;
C, through normal reaction flow process, the catalyst successively in counterweight gasoline hydrogenation reactor, pre-hydrogenation deactivation reaction of Salmon-Saxl device and selective hydrogenation reactor carries out sulfuration;
After D, heavy petrol hydrogenation reaction product flow through heat exchanger heat exchange, through heavy fractioning hydrogenation product air cooler, water cooler cooling, enter cold high pressure separator and carry out gas-liquid separation;
In described method: hydrogenation catalyst is the hydrogenation catalyst in liquid-phase hydrogenatin technique, vulcanizing agent injection rate is 20-90 kg/h, cure time is 10-48 h, direct steaming gasoline is from the surge tank of raw material surge tank and heavy naphtha, and system is introduced new hydrogen and is set up hydrogen circulation, and hydrogen-oil ratio is 180-300 Nm
3/ m
3, heavy petrol hydrogenation reactor heat is provided by reaction feed stove, and pre-hydrogenation deactivation reaction of Salmon-Saxl device heat, through selective hydrogenation product/heavy fractioning hydrogenation product exchanger, is provided by heavy fractioning hydrogenation product; Selective hydrogenation reactor institute calorific requirement, through catalytic gasoline/pre-hydrogenation product exchanger, is provided by pre-hydrogenation products.
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